Paraffin reaction



Patented Sept. 22, 1942 PARAFFIN- REACTION Ober 'C. Slotterbeck, Clark Township, Union County, and Raphael Bosen, Elizabeth, N. J., assignors to Standard Oil Development Company, a corporation of Delaware No Drawing. Application December 15, 19 39, Serial-No. 309,406

11 Claims.

The present invention relates to the reaction of isoparaflins with other paraflinic hydrocarbons in the presence of a catalyst under conditions known to promote alkylation reactions.

In a co-pendingapplication, Ober C. Slotter beck, Serial No. 309,405 filed De'cember'15, 1939, there is described a novel alkylation catalyst consisting of a composition resulting from the saturation of a hydrogen fluoride-water mixture with boron fluoride. This catalyst as disclosed in that application is capable of effecting the I condensation of mono-oleflns with paraflinic hydrocarbons containing at least one tertiary carbon atom per molecule to produce saturated, branched-chain parafllns having valuable motor fuel properties. It has now been found that this catalyst is also capable of effecting a condensation of isoparaflins with other paraflinic hydrocarbons.

In general, it is known that the paraflinic hydrocarbons, especially the lower members of the ride, and water, under alkylating conditions.

It is an object of the present invention to react a paraflin containing at least one tertiary carbon atom per molecule with another paraffln, having either a straight-chain or branchedchain structure, in such a manner as to produce saturated liquid hydrocarbons.

It is a further object of'the invention to react relatively low octane number, liquid, parafflnic hydrocarbons having branchedand/or straight-chain structures with low-boiling paratfins containing at least one tertiary carbon atom per molecule to produce motor fuels of improved octane number.

It is a further object of this invention to proprecipitate formed therein.

apparent from the following description 'of'the invention are accomplished by introducing mixtures of paraffins such as those described above into an alkylation reactor under suitable alkylation conditions in the presence of a BFz-HzG-HF' catalyst composition.

The catalyst composition may be prepared by admixing water, boron fluoride and hydrogen fluoride in any manner. One method of manufacturing the catalyst composition involves the preparation of a saturated solution of boron fluoride in water and the introduction of anhydrous hydrogen fluoride or commercial hydrogen fluoride (usually at 48% aqueous solution) into this solution. Any desired amount of hydrogen fluoride may be introduced into the boron fluoride-water solution. The preferred procedure for making up the catalyst consists of introducing the desired quantity of hydrogen fluoride into water and then saturating this aqueous hydrogen fluoride solution with boron fluoride.'

In preparing the catalyst composition according to the former method, it is sometimes necessary to filter the catalyst composition to remove any Usually, no precipitate is formed in the preparation of the catalyst by the preferred procedure, so that, in this case, filtering is unnecessary. The catalyst compositions are prepared at room temperature. The exact nature 01 the catalyst is not known and its composition varies to some extent with the specific method used for its preparation.

Depending on the concentration of hydrogen fluoride present in the novel catalyst, the freezing point ofthe catalyst varies between about -15 C. and about +23 C. The temperatures employed for the reactions of the present invention may range from just above the freezing I point of the catalyst composition to about 200 C.

duce a mixture of liquid saturated hydrocarbons I suitable for use as motor fuels or as blending agents for motor iuels by reacting waste refinery gases, one constituent of which contains at least one tertiarycarbon atom per molecule,' with nor- .kylation conditions.

or even higher. However, it ispreferred. to opcrate; at temperatures between about 50 and about 120 C. When operating at the higher I temperatures, it is advantageous to employ superatmospheric pressures in order to maintain. the reactants in the liquid phase, since it has been foundthat eflicient contacting of the several reactants with each other and 'the catalyst is conqd-ucive to higher yields of the condensation products. Such contacting is more easly accom plished by intensive agitation whenthe react--.

The time of reants are in the liquidphase. action may vary between about 2.5 and about 30 hours, preferably being between about 10 and about 25 hours. The rate or conversion is con- These objects, as well as others which will be siderably higher at elevated reaction temperatures than at low reaction temperatures. Therefore, the time of contact may be adjusted so that a shorter time of contact will beemployed at the higher temperatures and a longer time of contact at the lower temperatures. It is ordinarily satisfactory to use reaction times of between about 5 hours and about hours when employing temperatures of between about 40 and about 120 C.

It is contemplated to carry out the reactions in either the liquid or vapor phase, although for a commercial operation it is preferred to employ superatmospheric pressures at least suflicient to maintain the reactants in the' liquid phase. Pressures of between about 1 andgabout 100 atmospheres may be employed. However,

pressures of between'about 3 and about 10 atmospreferred conditions and employing ordinary refinery hydrocarbon feed stocks, for example, field butanes and the like.

It has been found to be desirable to maintain a substantial excess of the hydrocarbon containing at least 1 tertiary carbon atom per molecule in the reaction zone. The molar ratio of the 'isoparafiin to the other paraflinic reactants may range from about 1:1 to about 3:1. However, it is preferred to operate with a reaction mixture containing the isoparaflin and theother paraflinic reactant in a molar ratio of between about 2:1 and about 10:1. In cases where both of the reactants are isoparafllnic in nature, it is preferred to have the isoparafiin of the lower boiling point present in substantial excess of the isoparaflin of the higher boiling point, although the operation may be-carried out in the presence of an excess of the higher boiling point isoparaflln.

The process of the present invention may suitably be carried out in any apparatus which has heretofore been employed for polymerization or alkylation processes, such as, for example, those pheres are. suflicient when operating under the employed when using concentrated sulfuric acid as the catalytic agent. The catalyst of this invention is liquid under the conditions of reaction and also immiscible with the hydrocarbon reactants and products. Conventional settling tanks may therefore be employed incommercial units for separating the partially spent catalyst .from' the product. Such catal'ytic material may then be returned to the alkylation reactor, as

theiso-octanes may be employed. Furthermore, mixtures of two or more of these hydrocarbons or mixtures of paraflinc hydrocarbons containing isoparaflins for example, aviation alkylate, having any desired boiling range, for example, 23.

through 145 0., prepared by alklating isobutane with butylenes in'the presence of concentrated sulfuric acid, or other low boiling alkylates, may

be employed. Likewise, alkylate bottoms, that is, the higher boiling alkylates, may be employed as feed stocks or as a portionof the feed stocks in the present process, in which case safety fuels are produced. The feed stock for the present process may be composed entirely of isoparaflins or mixtures of isoparafiins, as above set forth. However, normal parafiins may likewise be employed as reactants provided at least one isop'aramn containing at least one tertiary carbon atom per molecule is also present in the feed stock. Thus, for example, the feed stocks may .contain normal pentane, normal hexane,-

normal heptane, normal octane, normal nonane,

and their higher homologues or mixtures of two or more of these straight-chain parafiinic hydrocarbons. One suitable source of higher boiling,straight-chain parafiins is paraflin wax. Furthermore,

stocks for the present process. ber of straight run naphthas may be improved by contacting mixtures of straight run naphthas and isobutane, isopentane, mixtures of these, or mixtures of any of the above-mentioned isoparaffinic reactants with the catalyst composition under the conditions heretofore specified. Although the process of the present invention may be carriedout by reacting a. high boiling isoparaflinic constituent of the feed with a low boiling,

straight-chain paraflinic constituent, it is preferredto carry out the reaction with feed stocks in which the lower boiling reactants contain the tertiary carbon atoms.

Other sources of supply of suitable feed stocks are readily available to refinery operators. Thus, for example,'C4 and/or C5 cuts, from which the major portion of the olefins has been removed, may be employed in the feed stocks of the pres ent invention.v These refinery cuts may be obtained from catalytic and/or thermal cracking in the case of sulfuric acid alkylation processes. It is desirable, when employing the novel cata fractional distillation or other suitable means from the desired product andreturned in whole or a in part to the original reaction zone in order to materially increase the yields (based on the fresh parafiins fed to the unit) of the ,desired products. I

Any of the members of the paraflin series containing at least 1 tertiary carbon atom per units, from refinery stabilizer bottoms, from catalytic or thermal polymerization and/or polymerization processes, andthe like.

The process may be carried out either by a I batch or continuous type of operation, although it is preferred to carry out the process continu-' ously. Higher yields are obtained if the feed stock and the catalyst are intimately contacted under the condensation conditions. In the case of batch operations, mechanical stirrers or shakers provide adequate agitation. In the case of continuous operations, the use of turbo mixers,

molecule may be used as reactants in the present process. Thus, for example, isobutane, isopentane, the lsohexanes, the isoheptanes, and

the introduction of the feed into the reactor through jets of restricted internal diameter or porous thimbles, orthe like results in ample agitation of the reaction mass.

The novel catalyst gradually becomes less effective for promoting the condensation reaction as its length of service increases. This is partially due to a gradual dilution of the catalyst by water introduced in small amounts with the hydrocarbon feed, and high molecular weight hydrocarbons which do not readily separate from the catalyst during the ordinaryqoperation of the process. The catalyst concentration may be maintained to some extent by the addition of straight run naphthas and 'field 'butanes are'suitable sources of paramns for feed The octane numsmall amounts of hydrogen fluoride and/or boron fluoride either continuously or intermittently, to

the catalyst composition as it is being returned to the reaction zone from the catalyst-hydrocarbon settler. However, after prolonged usage, the

physical means, such as distillation or solvent extraction, or a chemical means, such as the use of dehydrating agents. However, the preferred procedure for regenerating the catalyst involves the addition of an amount of hydrogen fluoride to the catalyst layer suflicient to bring the hydrogen fluoride content of the catalyst up to its original value and a subsequent similar addition of boron fluoride. Such a procedure is more preferable than one involving the addition of boron fluoride followed by the addition of hydrogen fluoride or a procedure wherein hydrogen fluoride and boron fluoride are added simultaneously to the catalyst layer.

A modified procedure for the regeneration of the catalyst embodies a partial removal of the excess water by either mechanical or chemical means and the subsequent addition of hydrogen fluoride followed by the addition of boron fluoride to the catalyst layer. cedure is employed when it is desired to maintain the volume of regenerated catalyst constant with respect to the volume of the spent' catalyst withdrawn from the condensation system.

The following examples are intended to be illustrative of the invention described herein but are not to be considered as in any way limiting the scope of the appended claims.

Example 1 A mixture of 50 grams of iso-octane (2,2,4-

'trimethyl pentane) and 130.4 grams of iso-pen- -Such a combined prowater may be removed from the catalyst by a 145 C. and were substantially completely saturated in character. To the mixture of isopentane and alkylate bottoms were added 123.5 grams of catalyst, prepared by adding grams of 48% aqueous hydrogen fluoride to 100 grams of water and saturating the solution with boron fluoride. The catalyst composition contained 9.7% of hydrogen fluoride and 69.7% of boron fluoride, the remainder being water. This catalyst-hydrocarbon mixture was introduced into a reaction bomb, which was maintained at about 50 C. to about 60 C. and vigorously shaken for about 24 hours. Aproduct yield of about 174 weight per cent, based upon the alkylate bottoms introduced into the reactor, was obtained.

Ezcample 3 A mixture of 217.3 grams of isopentane and 50 grams of normal heptane, together with about 24% by volume of a catalyst prepared by adding.

100 grams of a 48% aqueous hydrogen fluoride solution to 25 grams of water and saturating the mixture with boron fluoride, was introduced into an autoclave, which was maintained at a temperature of about 100 C. to about 106 C,

and vigorously shaken for about 19 hours. Theyield of product boiling above 40 C. amounted to about 124 weight per cent, based upon the normal heptane in the reaction mixture.

Having described fully the invention and having set forth the nature and objects of the invention and illustrated the same, what is claimed as new and useful and desired to be secured by Letters Patent is:

1. A process for the production of branchedchain paraflins boiling within the gasoline range which comprises reacting at least one paraflln containing at least one tertiary carbonatom perv molecule with another paraflin of higher molecular weight in the presence of a catalyst pretion of boron fluoride; a crystalline precipitate v formed during the preparation of the catalyst and was removed by filtration. The autoclave was maintained at a temperature of between about 55 C. and'60 C. fora period of about 16 hours. During this shaken vigorously.

time, the autoclave was At .the end of this period, the hydrocarbon layer was separated from the pared by introducing hydrogen fluoride into water and saturating the resultant mixture with boron fluoride, the reaction being carried out under'alkylating conditions.

3. A process for the production of paraflinic motor fuels ofimproved octane number which comprises reacting paraflinic hydrocarbon mix tures boiling in the motor fuel range and of relatively low actane number with at least one parreaction mixture and was fractionated. .A '154 weight per cent yield (based upon the 2,2,4-trimethyl pentane charged) of product-above 40 C. was obtained.

Example 2 130.4 grams of isopentane were admixed with '50 grams of allavlated bottoms, obtained.from

aflin containing at least one tertiary carbon atom per molecule in the presence of a catalyst prepared by admixing only hydrogen fluoride, water,

and boron fluoride, "the reaction being carried out under alkylating conditions.

LA process as in claim 2 wherein the reac- I tiontemperature is between about the freezing point of the reaction mixture and about 200 0.,

sumcient pressure being applied to maintain the reaction mixture in the liquid phase.

5. A process as in claim 2 wherein the reac tion temperature is between about the freezing 6. A process for the production of branchedchain parafiins which comprises contacting an isoparaflin containing at least one tertiary carbon atom per molecule with an alkylate having an initial boiling point of 145 C. in the presence 100 c. with vigorous agitation miabout '19 hours in the presence at a catalyst composition prepared by adding aqueous HF to water and saturating the mixture with BFa. p

10. A process as in claim 9 wherein the isopentane: n-hexane molar ratio is between about 2:1 and about 10:1.

11. A process for the production branchedchain paraflins boiling within" the gasoline range cut, containing isobutane and isopentane, the

. time of contact being between about 10 and about hours. a

9. A process for the production of branchedchain paraflins which comprises reacting isopentane with n-hexane at a temperature of about which comprises contacting a refinery C4 cut containing isobutane and normal butane with a straight run naphtha with vigorous agitationat a temperature of between about and about 1 2 0 C., for from about 10 to about 25 hours in the presence of a catalyst composition prepared only from HF, H10, and BFa, and recovering the desired motor fuel fractions.

OBER c. SLOTIERBECK. RAPHAEL ROSEN. 

